Intramolecular crosslinking of poly(vinyl alcohol)

Poly(vinyl alcohol) is crosslinked in dilute solution (c=0.1 wt%) with glutaraldehyde. The reaction product is characterized by viscometry and gel permeation chromatography (g.p.c.). The intrinsic viscosity decreases with increasing degree of crosslinking and does not depend on temperature. G.p.c. reveals that the reaction product is not homogeneous, but consists of a mixture of particles with different sizes, possibly both intra- and intermolecularly crosslinked molecules. The intramolecularly crosslinked molecules are smaller in size than the initial polymer molecules and their size depends on the degree of crosslinking. They possess a narrow particle size distribution even if the initial polymer sample had a broad molecular weight distribution.     

Stochastic molecular descriptors for polymers. 4. Study of complex mixtures with topological indices of mass spectra spiral and star networks: The blood proteome case

The Quantitative Structure-Property Relationships (QSPRs) based on Graph or Network Theory are important for predicting the properties of polymeric systems. In the three previous papers of this series (Polymer 45 (2004) 3845-3853; Polymer 46 (2005) 2791-2798; and Polymer 46 (2005) 6461-6473) we focused on the uses of molecular graph parameters called topological indices (TIs) to link the structure of polymers with their biological properties. However, there has been little effort to extend these TIs to the study of complex mixtures of artificial polymers or biopolymers such as nucleic acids and proteins. In this sense, Blood Proteome (BP) is one of the most important and complex mixtures containing protein polymers. For instance, outcomes obtained by Mass Spectrometry (MS) analysis of BP are very useful for the early detection of diseases and drug-induced toxicities. Here, we use two Spiral and Star Network representations of the MS outcomes and defined a new type of TIs. The new TIs introduced here are the spectral moments (π_k) of the stochastic matrix associated to the Spiral graph and describe non-linear relationships between the different regions of the MS characteristic of BP. We used the MARCH-INSIDE approach to calculate the π_k(SN) of different BP samples and S2SNet to determine several Star graph TIs. In the second step, we develop the corresponding Quantitative Proteome-Property Relationship (QPPR) models using the Linear Discriminant Analysis (LDA). QPPRs are the analogues of QSPRs in the case of complex biopolymer mixtures. Specifically, the new QPPRs derived here may be used to detect drug-induced cardiac toxicities from BP samples. Different Machine Learning classification algorithms were used to fit the QPPRs based on π_k(SN), showing J48 decision tree classifier to have the best performance. These results suggest that the present approach captures important features of the complex biopolymers mixtures and opens new opportunities to the application of the idea supporting classic QSPRs in polymer sciences.     

Breakdown of oil films and formation of residual films

The breakdown processes of oil films under quasi-static loading have been investigated by using a newly developed steel-oil-mercury system. The relationship between the thickness and breakdown ratio of a hexadecane film is represented by a single master curve independently of the indentation speed, indentation load, and temperature. The master curve shows that the breakdown process of hexadecane includes two stages; one is the decrement of the thickness without breakdown and the other is the decrement of the thickness with a drastic progress of breakdown. By solving a small amount of fatty acid in hexadecane, the thickness increases and the breakdown ratio decreases noticeably; a multilayer residual film supporting normal load is formed between two metal surfaces. Experiments at different temperatures reveal a negative relationship between the temperature and thickness of residual film, which indicates that the residual film is organized by physical interaction rather than chemical interaction. At least under a lower concentration, the residual film appears to consist of not only fatty acid molecules but also hexadecane molecules.     

Characterization of rheological properties of systems containing sugar substitutes and carrageenan

The effects of addition of κ-carrageenan to solutions containing 40% (w/w) sugar substitute on the rheological properties of these systems were investigated at 25 °C using a rotational viscometer at rotational speeds of 6, 12, 30, and 60 rev min⁻¹. The flow behaviour of the solutions was adequately described by the power law model with or without yield stress. The consistency index ( K ) and the flow behaviour index ( n ) were determined from shear stress vs. shear rate data. The flow parameters of the solutions depended on the carrageenan concentration. The apparent viscosities of the systems decreased with increasing shear rate, indicating pseudoplastic behaviour. The final carrageenan concentration was found to be an effective factor controlling the degree of sliminess of the model food systems studied.     

Effects of viscosity on the bitterness and astringency of grape seed tannin

To examine the separate effects of viscosity and sweetness on astringency, aqueous solutions of grape seed tannin (GST) were thickened with carboxymethyl cellulose (CMC) from 2 to 45 cP (experiment 1) or sweetened with 0 to 1.8 g/L aspartame (experiment 2). Trained subjects continuously rated astringency and bitterness in duplicate. Subjects were categorized by the salivary flow induced by citric acid and ability to taste n-propyl thiouracil (PROP). In experiment 1, maximum intensity and total duration of astringency were significantly decreased as viscosity rose, although time to maximum intensity of astringency was not affected. Maximum intensity and total duration of bitterness were not significantly affected by increasing viscosity; however, the onset of bitterness was significantly delayed. In experiment 2, increasing sweetness had no affect on any astringency parameter, although maximum intensity of bitterness was significantly decreased. Neither PROP nor salivary flow-status had any effect on perception of bitterness or astringency in either experiment.     

Linear viscoelastic properties of mixtures of 3- and 4-arm polybutadiene stars

The viscoelastic properties of a three-arm and a four-arm star polybutadiene with the same arm molecular weight (M_a) were studied. The zero-shear recoverable compliance (J⁰_e) and plateau modulus (G⁰_N) for these stars are the same. The zero-shear viscosity (η₀) of the three-arm star is 20% lower than that of the four-arm star. Mixtures of the stars had J⁰_e and G⁰_N unchanged. A $\text{50}\text{50}$ mixture of the three- and four-arm star was diluted with a low molecular weight linear polybutadiene. G⁰_N∝ø²; J⁰_e∝ø^?1 and M_e∝ø^?1, as expected for dilution with a θ-solvent.     

Characterization of the flow behaviour of sausage emulsions with a simple tube viscometer

A specially designed tube viscometer was used to measure apparent viscosity during flow of Bologna type sausage emulsions moving through a pipe. Emulsions varied in fat content (from 21.8 to 44.3%) and in moisture/protein ratio (from 3.7 to 5.6), and the effects of added sodium chloride, sodium diphosphate, starch and blood plasma were investigated in a 36% fat, 3.7 moisture/protein emulsion.
The shear stresses determined as a function of shear rate were fitted by a power law. Yield stress of the emulsions was negligible relative to the applied stress. However, inspection of the flow profiles indicated that considerable slip of the sausage emulsion occurred at the pipe wall. Both emulsion flow and slip contribute to overall flow behaviour, so a kind of effective viscosity is determined. Intrinsic rheological properties and wall slip will both be affected by the composition of the sausage emulsion.     

Rhizobium trifolii capsular polysaccharide: a novel biopolymer with striking physical properties

The physical properties of the capsular polysaccharide of Rhizobium Trifolii (CPS) were investigated. Viscosity measurements provided information about the hydrodynamic volume of single coils, the perturbation of solvent flow and the shear-thinning behaviour of concentrated solutions. Changes in chain geometry and the development of an intermolecular network as a function of temperature were monitored using the techniques of optical rotation and dynamic oscillation. Finally, analysis of calorimetric thermograms elucidated the type of interactions between CPS and the bacterial levan. Overall, the Rhizobium polysaccharide was found to form thermally-reversible gels at an extremely low 'minimum critical gelling concentration' (c_o∼ 0.35gl^-1). At temperatures above the gel melting point (∼ 48°C), however, the compact polymer coils entangled at comparatively high concentrations (about 60 times higher than c_o). In the presence of a highly branched levan, the thermal stability of ordered CPS structures increased as a consequence of thermodynamic incompatibility between the two polymers.     

辐射对血液流变效应的研究及动物全身照射后全血粘度的变化规律

本文结果表明经一次大剂量全身照射后的机体血液流变的主要特性为全血表观粘度先高粘后低粘的双向性变化,从照后第一天起即升高。随着放射病病程的发展,在早期有一个高粘峰,其峰均值比照前升高47.80％。但因不同动物、不同剂量、不同均速,不同血源而变化不同。     

Synthesis and aqueous solution behaviors of sodium sulfonate‐terminated dendritic poly(ester‐amine)

Sodium sulfonate‐terminated dendritic poly(ester‐amine) (SPEA) was synthesized by sulfonation of acrylic double bond‐terminated dendritic poly(ester‐amine) (APEA) with sodium hydrogen sulfite (NaHSO₃) in mixture of diglycol and 2‐butanone under normal pressure. The structure of SPEA was characterized by IR, ¹H‐NMR, and elemental analysis. SPEA was water‐soluble. 1.0–40.0% (mass) SPEA aqueous solutions appeared as dilatant fluid. When pH value varied from 1.5 to 12.0, the viscosity of 1–5% (mass) SPEA aqueous solutions changed very small, and the electric conductivity almost kept stable within pH 3.0–10.0. The relationship between the viscosity and the concentration of SPEA water solutions was similar to that of NaCl water solutions. The surface tension of SPEA water solutions was lower than that of polyethylene glycol 2000 water solutions with the same concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008